Soluble alkoxy-group substituted aminobenzenesulfonic acid aniline conducting polymers

ABSTRACT

A soluble aniline conducting polymer characterized in that said conductive polymer comprises as a repeating unit an alkoxyl group-substituted aminobenzenesulfonic acid, its alkali metal salts, ammonium salts and/or substituted ammonium salts, and is a solid having a weight average molecular weight of about 1900 or more at room temperature, a conductive composition and electric conductor comprising the same, and a method for producing a soluble aniline conducting polymer having a weight average molecular weight of 10,000 t 3,240,000 characterized by polymerizing at least one compound (1) selected from the group consisting of an acidic group-substituted aniline, its alkali metal salts, ammonium salts and substituted ammonium salts in a solution containing a basic compound (2) using an oxidizing agent.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a solvent-soluble aniline conductingpolymer, a method for producing the same, a conductive composition withthe same, an electric conductor formed from the conductive compositionand a method for producing the same. A solution and conductivecomposition produced from the polymer of the present invention can beapplied to various uses for static charging prevention by simpletechniques such as coating, spraying, casting, dipping and the like.

The electric conductor of the present invention obtained from the aboveconductive composition can be used in various uses described below:

Industrial packing materials for semiconductors, electric and electronicparts, etc.; static charging preventing films for recording materialsfor electrophotography such as films for overhead projectors, slidefilms, etc.; static charging prevention for magnetic recording tapessuch as audio-tapes, video-tapes, tapes for computers, floppy discs,etc.; static charging prevention for the surface of input and displaydevices such as transparent touch panels, electroluminescence displays,liquid crystal displays and the like; and transparent conductive filmsor glass used as a transparent electrode, various kinds of sensor, etc.

2. Description of the Related Art

A doped polyaniline (conducting polymer) is well known, but it isinsoluble in most solvents, so that it has difficulties in molding andfabricating. A method of polymerizing aniline by electrolytic oxidation[Japanese Patent Application Kokai No. 60-235831; J. Polymer Sci.Polymer Chem. Ed., 26, 1531 (1988)] can form a polyaniline film on anelectrode, but it has problems that the isolation of the film istroublesome and also mass synthesis is difficult.

In recent years, there are proposed an alkali-soluble sulfonatedpolyaniline which develops conductivity without addition of dopingagents, its synthesis method, a carboxylated polyaniline and itssynthesis method.

For example, the following methods are known as synthesis methods forthe sulfonated polyaniline; A method of synthesizing a sulfonatedpolyaniline electrochemically polymerizing aniline andm-aminobenzenesulfonic acid (Nihon Kagaku-kaishi, 1985, 1124; JapanesePatent Application Kokai No. 02-166165); a method of synthesizing asulfonated polyaniline by electrochemically polymerizing each alone ofo-, m- and p-aminobenzenesulfonic acids [Preprint of the 64th AutumnAnnual Meeting of Nihon Kagaku-kai, Vol. II, 706 (1992)]; a method ofsynthesizing a sulfonated polyaniline by chemically polymerizing anilineand o- and m-aminobenzenesulfonic acids (Japanese Patent ApplicationKokai No. 01-301714); a method of polymerizing a monomer containing anaminobenzenesulfonic acid compound or that compound and an anilinecompound by chemical oxidation (Japanese Patent Application Kokai No.6-56987); a method of sulfonating with conc. sulfuric acid anemeraldine-type polymer (polyaniline) obtained by chemical orelectrochemical polymerization (EP 96319); a method of sulfonating witha sulfuric anhydride/triethyl phosphate complex (Japanese PatentApplication Kokai No. 61-197633); a method of sulfonating with a fumingsulfuric acid [J. Am. Chem. Soc., (1991)113, 2665-2671; J. Am. Chem.Soc., (1990)112, 2880; WO91-05979, WO91-06887; Japanese PatentApplication Kokai No. 6-145386]; a method of synthesizing anN-substituted sulfonated polyaniline by chemically polymerizingdiphenylamine-4-sulfonic acid (sodium salt) [Polymer, (1993)34,158-162], and the like.

The above method of synthesizing a sulfonated polyaniline byelectrochemically polymerizing aniline and m-aminobenzenesulfonic acid(Nihon Kagaku-kaishi, 1985, 1124; Japanese Patent Application Kokai No.02-166165 and EP-253595) forms a product on an electrode, so that it hasproblems that an isolation operation is troublesome and also masssynthesis is difficult.

In the above-mentioned Preprint of the 64th Autumn Annual Meeting ofNihon Kagaku-kai, Vol. II, 706 (1992), there is reported a method ofsynthesizing a soluble conducting polymer by electrolytic oxidation ofan aminobenzenesulfonic acid, but it is also difficult to say that thismethod is suitable for mass synthesis, and further a problem stillremains in the performance of the resulting polymer. Also, there is adescription that the desired product was not obtained when the chemicaloxidation polymerization of an aminobenzenesulfonic acid was carried outwith ammonium peroxodisulfate as an oxidizing agent. In J. Am. Chem.Soc., (1991)113, 2665-2671, there is a description that chemical andelectrochemical polymerizations of o- and m-aminobenzenesulfonic acidswere tried with no success.

In Japanese Patent Application Kokai No. 6-56987, there is a descriptionthat a water-soluble conducting polymer is obtained by carrying out thechemical oxidation polymerization of a monomer containing anaminobenzenesulfonic acid compound, or that compound and an anilinecompound, in any of acidic, neutral and alkaline solutions.

However, the present inventors' investigation shows that, in order toobtain a polymer having a sufficiently high molecular weight for filmformation, it is an essential condition to carry out the polymerizationin the presence of a basic compound, and that such a high molecularweight polymer cannot be obtained in acidic and neutral solutions.

In Japanese Patent Application Kokai No. 6-56987, all the examplesdescribe polymerization in a sulfuric acid-containing acidic solution,not in an alkaline solution. Even in examples describing thepolymerization in an acidic aqueous solution, there are no data on themolecular weight, so that any physical properties of the polymersobtained are not clear.

Further, the present inventors tried the polymerization in a protonicacid-containing aqueous solution and a simple aqueous solution usingammonium peroxodisulfate as an oxidizing agent. As a result, awater-soluble polymer was obtained, but its molecular weight was so lowthat such a practical polymer that forms a film was not obtained.

The present inventors traced the method described in Japanese PatentApplication Kokai No. 01-301714, wherein aniline andm-aminobenzenesulfonic acid are chemically polymerized using ammoniumperoxodisulfate, and the method described in Japanese Patent ApplicationKokai No. 6-56987, wherein aniline and m-aminobenzenesulfonic acid arechemically polymerized using potassium permanganate. It was found,however, that about only one sulfonic group per five aromatic rings wasintroduced, and that the resulting polymer showed a high conductivity,but it was completely insoluble in neutral and acidic water and almostinsoluble in alkaline aqueous solutions such as aqueous ammonia. Also,when sulfonation is carried out by a method described in Japanese PatentApplication Kokai No. 61-197633, about only one sulfonic group per fivearomatic rings is introduced as described in page 7 of that literature,because the solubility of polyaniline in a sulfonation solvent is not sosufficient that the reaction is carried out in a dispersion state. Thesulfonated polyaniline thus obtained has an introduced sulfonic group atonly a low rate and has problems of the conductivity and solubilitybeing not sufficient.

Also, according to J. Am. Chem. Soc., (1991)113, 2665-2671 and J. Am.Chem. Soc., (1990)112, 2800, it is described that when a polyaniline issulfonated with fuming sulfuric acid, about one sulfonic group per twoaromatic rings is introduced. When, however, sufficient sulfonation ofpolyaniline is tried by this method, a large excess of fuming sulfuricacid is required because the solubility of polyaniline in fumingsulfuric acid is not sufficient. Also, there is a problem that thepolymer is easy to solidify when polyaniline is added to fuming sulfuricacid. These problems make a manufacturing process troublesome, andincrease the cost of the final product. Further, the polymer andsulfonated product synthesized by the above methods have problems thatthey are insufficient in conductivity, and that they are soluble inaqueous solutions containing a base (e.g. ammonia, alkylamine), butinsoluble in water itself.

According to Polymer (1993)34, 158-162, it is described that whendiphenylamine-4-sulfonic acid (sodium salt) is polymerized, anN-substituted sulfonated polyaniline in which one benzenesulfonic grouphas been introduced into the aniline skeleton is obtained, and that thisproduct is soluble in water itself, but supercentrifugation operation isnecessary to isolate the resulting polymer. The present inventors tracedthis method to find that since this polymer has a high solubility, theyield of the polymer from the polymerization solvent is low, andtherefore that when a high-speed centrifugation operation is notapplied, the polymer cannot be isolated. Also, it was found that sincethis polymer is of an N-substituted type, the conductivity of thispolymer is low as compared with a polymer synthesized by a methoddescribed in J. Am. Chem. Soc., (1991)113, 2665-2671.

Also, a synthesis method for a carboxylated polyaniline is proposed, inwhich 2- or 3-carboxyaniline or its salt is oxidation polymerized, andthe resulting product is treated with a basic substance to obtain thecarboxyl group in the form of salt (Japanese Patent Application KokaiNo. 4-268331). In this method, the amount of the oxidizing agentrequired is twice or more by equivalent that of the raw material, andalso the value of conductivity is low. This is considered to show thatthe reactivity of the monomer is low, and therefore a low molecularweight polymer is produced.

Also, a synthetic method is proposed in which methyl anthranilate(anthranilic acid methyl ester) is polymerized in an aqueous acidicsolvent in the presence of ammonium peroxodisulfate, and then the methylester is saponified with alcoholic potassium hydroxide (Japanese PatentApplication Kokai No. 5-226238). This reaction is carried out in twosteps, so that operation is very troublesome.

Further, the present inventors tried polymerization of 2-carboxyanilinein a protonic acid-containing aqueous solution using ammoniumperoxodisulfate as an oxidizing agent, but the product could not beobtained. Also, the present inventors tried polymerization of anilineand 2-carboxyaniline in a protonic acid-containing aqueous solutionusing ammonium peroxodisulfate as an oxidizing agent, but the copolymerobtained was low in both solubility and conductivity. This is consideredto show that the proportion of copolymerized 2-carboxyaniline in thecopolymer obtained is low.

When formability such as film formation by coating is taken intoaccount, in order that coating onto, particularly, any of hydrophilicand hydrophobic base materials may be possible, it is desired to havesolubility in both water and organic solvents. However, the sulfonatedproduct of polyaniline has solubility in an alkali water, but it isinsoluble in neutral to acidic aqueous solutions, and also itssolubility in organic solvents is not sufficient.

As a method to solve these various problems, the present inventorsproposed a method for producing the sulfonated product of anilinecopolymers characterized in that at least one compound selected from thegroup consisting of aniline, N-alkylaniline and phenylenediamines iscopolymerized with aminobenzenesulfonic acid in acidic solvents using anoxidizing agent, and then the resulting copolymer is sulfonated with asulfonating agent (DE-4244360). The resulting anilne conducting polymercontains a sulfonic acid group in a rate of 15 to 80% based on the totalaromatic rings. However, this method also requires sulfonation operationin conc. sulfuric acid, so that treatment of the waste acid remains as aserious problem. Further, there is a problem of the resulting copolymerbeing insoluble in water itself.

Any of the copolymers synthesized by the above methods is presumed tohave a structure represented by the following formula (9), ##STR1##wherein each of R₁₁, R₁₂, R₁₃ and R₁₄ is selected from the groupconsisting of hydrogen and a sulfonic acid group, R¹ is selected fromthe group consisting of hydrogen and a C₁ -C₄ alkyl group, the rate ofsulfonic acid groups is 40 to 80% based on the aromatic ring, Xrepresents a number of from 0 to 1, and n represents a number of from 2to 1500 showing a polymerization degree.

The polymerization solvent used in the above chemical polymerization iswater or aqueous solutions containing a protonic acid. For example, theforegoing Japanese Patent Application Kokai No. 1-163263 describes thatwhen ammonium peroxodisulfate is used as an oxidizing agent, it isdesirable to contain a protonic acid having a pKa of, particularly, 3 orless, and that in the polymerization of aniline, those which candissolve aniline, a protonic acid and oxidizing agent and also are notoxidized by the oxidizing agent are used as a solvent. Also, in Example3 of the foregoing Japanese Patent Application Kokai No. 4-268331,oxidation polymerization is carried out by dissolving 4 g of sodiumanthranilate in 100 ml of water and then adding a solution of 22.7 g ofammonium peroxodisulfate in 100 ml of water to the above aqueousanthranilic acid solution. The pH of this polymerization solvent is alsonearly neutral, and it did not occur to anybody from the properties ofthe polymerization system to positively make alkaline the polymerizationsolvent and oxidation polymerization system from the standpoint ofimprovement in the reactivity of the monomer.

A method disclosed in Japanese Patent Application Kokai No. 4-268331requires a step for treating a product with a basic substance afteroxidation polymerization. Japanese Patent Application Kokai No. 6-56987describes that in polymerization in alkaline systems, an additional acidtreatment step is required in order to make the resulting polymer highlyconductive. However, the method of the present invention requires suchno aftertreatment step, so that there is a merit that the manufacturingprocess can be reduced by one step.

Examples of the conductive components of the conventional conductivecompositions include conducting polymers such as7,7,8,8-tetracyanoquinodimethane (TCNQ) complex, polyaniline, etc.,those using a metallic powder or carbon powder and a surface activeagent, and compositions produced by combining these components andpolymer compounds. Examples of the known electric conductors includethose formed on a base material using conductive paints comprising theforegoing compositions.

For example, a method of forming metal thin films comprising gold,platinum, etc. and metal oxide thin films comprising indium tin oxide(ITO), etc. on base materials (e.g. plastic film, glass) using an ionbeam sputtering apparatus or vacuum deposition apparatus, is known as amethod of obtaining electric conductors having excellent transparencyand conductivity. However, the apparatus used to form the thin films areexpensive, and yet noble metals (e.g. gold, platinum), ITO, etc. used asa material are also expensive, so that there is a problem that theresulting electric conductors become also expensive.

The presently known electron-conductive high-molecular electricconductors with TCNQ include those comprising a polymer compound havinga quaternary nitrogen-containing cationic group and TCNQ. These electricconductors are very poor in solubility in solvents, and many of them aresoluble only in special solvents such as dimethylformamide, etc. It istherefore difficult to say that these electric conductors are suitableas a varnish.

Conducting polymer compositions comprising a polymer compound and theorganic low-molecular complex of TCNQ are proposed (Japanese PatentApplication Kokoku No. 44-16499, and Japanese Patent Application KokaiNo. 50-123750, No. 54-130651 and No. 1-210470). As to electricconductors obtained by this method, it is thought that the crystals ofthe TCNQ complex grow in the polymer compound, and that the conductivityof the electric conductors more improves as the degree of overlapping ofthese crystals becomes larger. However, the state of this crystal growthis easily affected by the rate of volatilization of a solvent andtemperature distribution at the time of drying. Therefore, the number ofconductive passages per unit area becomes non-uniform to make thedispersion of surface resistance large, so that uniform surfaceresistance cannot be obtained. Besides, if there is even a slightdeterioration of the points of bonding of the crystals inhigh-temperature conditions (e.g. heating to 140° C.) orhigh-temperature high-humidity conditions (e.g. 60° C.×95% RH), thereoccurs a problem that the number of the conductive passages largelyreduces and the conductivity also largely reduces.

A doped polyaniline (conducting polymer) is well known, but it isinsoluble in most solvents, so that it has difficulties in molding andfabricating. A method of polymerizing aniline by electrolytic oxidation[Japanese Patent Application Kokai No. 60-235831; J. Polymer Sci.Polymer Chem. Ed., 26, 1531 (1988)] can form a polyaniline film on anelectrode, but it has problems that the isolation of the film istroublesome and also mass synthesis is difficult.

On the other hand, there is a report on conductive compositionscomprising a polyaniline in an undoped state obtained by chemicaloxidation polymerization of aniline and the ammonium salt of a protonicacid having an acid dissociation constant, pKa, of 4.8 or less (JapanesePatent Application Kokai No. 3-285983). However, the polyaniline in theundoped state is soluble only in special solvents such asN-methyl-2-pyrrolidone, so that it is difficult to say that thepolyaniline is suitable for a varnish.

Further, the foregoing electric conductor is formed with organicsolvents, so that when these solvents are a dangerous substance havingproperties such as inflammability, explosiveness, etc., there areproblems such as safety to working environments and the like. Further,with an increasing interest in safety to human body with respect to thetoxicity of solvents and environmental problem on the earth, regulationson various organic solvents exerting adverse effects on human body andenvironment are being strengthened, so that the safety of conductivecompositions is also becoming a serious problem.

In recent years, there are proposed an alkali-soluble sulfonatedpolyaniline developing conductivity without addition of dopants and itssynthesis method, and conductive compositions with it are also reported.For example, conductive compositions comprising the above alkali-solublesulfonated polyaniline and a polymer compound are reported (U.S. Pat.No. 5,109,70). However, the polymer compound used is poly(1,4-benzamide)resins, polyimide resins, etc. which are extremely low in solubility inorganic solvents, and also sulfuric acid, etc. are used as a solvent.Therefore there remains a serious problem in using the compositions asones for varnish. Also, conductive compositions with such an anilineconducting polymer as described hereinbefore are known. Since, however,the polymer itself has difficult points, use as conductive compositionsis also a question.

The electric conductor comprising a carbon powder or metallic powder anda polymer compound is excellent in durability of coating film, but thereis a problem that the coating film lacks transparency. Electricconductors are known in which conductivity has been given the surface oftheir plastic film by kneading a translucent anionic, cationic, nonionicor amphoteric surface active agent into the film, or coating the agentonto the surface of the film, thereby giving hydrophilic property andionic property. Since, however, the electric conductor obtained by thismethod is ion-conductive, there are problems that the ion conductivityis subject to the effect of humidity in the atmosphere, and also thatconductivity, i.e. the surface resistance per unit area, cannot be made10⁸ Ω/□ or less.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a soluble anilineconducting polymer which develops a high conductivity, shows excellentsolubility in water having any pH or organic solvents and has animproved coating property.

Another object of the present invention is to provide a conductivecomposition having no temperature dependence, developing a highconductivity and having excellent film-forming property, moldability andtransparency, and an electric conductor having a small dispersion ofsurface resistance.

The present inventors have extensively studied a method for producingacidic group-substituted polyanilines in which the acidic group has beenintroduced at a high rate in order to obtain a high conductivity andsolubility, the example of such acidic group-substituted polyanilinesincluding a sulfonated polyaniline in which the ratio of the introducedsulfonic group to the aromatic ring is large, and a carboxylatedpolyaniline in which the ratio of the introduced carboxyl group to thearomatic ring is large. As a result, the present inventors have foundthat when an acidic group-substituted aniline such as a sulfonic acidgroup-substituted aniline or a carboxyl group-substituted aniline ispolymerized using an oxidizing agent in a basic compound-containingsolution, that is, an alkaline polymerization solution, surprisingly,the reactivity remarkably improves, and a polymer having a highmolecular weight can be produced from the conventional anilines having asulfonic or carboxyl group, contrary to an established theory thatchemical oxidation polymerization of such anilines is difficult bythemselves. Besides, the resulting conducting polymer shows a highconductivity, dissolves in aqueous solutions having any pH from an acidto alkali, particularly dissolves in water itself, and further showsexcellent solubility in organic solvents such as alcohols.

The present invention relates to a soluble aniline conducting polymercharacterized by being a polymer having as a repeating unit an alkoxylgroup-substituted aminobenzenesulfonic acid, its alkali metal salt,ammonium salt and/or substituted ammonium salt, and being a solid havinga weight average molecular weight of about 1900 or more at roomtemperature.

The present invention relates to a conductive composition comprising awater-soluble aniline conducting polymer (a) and a solvent (b), or theabove components (a) and (b) and at least one polymer compound (c)selected from the group consisting of water-soluble polymer compoundsand polymer compounds which form an emulsion in an aqueous system,and/or at least one nitrogen-containing compound (d) selected from thegroup consisting of amines and quaternary ammonium salts.

Also, the present invention relates to an electric conductor comprisinga transparent conducting polymer film comprising a water-soluble anilineconducting polymer (a), or that polymer (a) and at least one polymercompound (c) selected from the group consisting of water-soluble polymercompounds and polymer compounds which form an emulsion in an aqueoussystem, and/or a surface active agent (e).

Also, the present invention relates to a method for producing anelectric conductor comprising coating the following conductivecomposition (i), (ii) or (iii), for example, onto at least one surfaceof a base material to form a transparent conducting polymer film, andallowing the film to stand at room temperature or heat-treating the filmto remove the components (b) and (d) by volatilization, the aboveconductive composition (i) comprising a water-soluble aniline conductingpolymer (a) and a solvent (b); the above conductive composition (ii)comprising the components (a) and (b), at least one polymer compound (c)selected from the group consisting of water-soluble polymer compoundsand polymer compounds which form an emulsion in aqueous systems, and/orat least one nitrogen-containing compound (d) selected from the groupconsisting of amines and quaternary ammonium salts; and the aboveconductive composition (iii) comprising the foregoing composition (i) or(ii) and a surface active agent (e).

Also, the present invention relates to a method for producing a solubleaniline conducting polymer characterized in that at least one compound(1) selected from the group consisting of an acidic group-substitutedaniline, its alkali metal salts, ammonium salts and substituted ammoniumsalts is polymerized with the aid of an oxidizing agent in a solutioncontaining a basic compound (2).

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a chart obtained in the measurement of the molecular weight ofthe conducting polymer synthesized in Example 1.

FIG. 2 is a UV-visible spectrum measured in a range of from 190 nm to900 nm of the conducting polymer synthesized in Example 2 in a 0.1mole/liter aqueous sulfuric acid solution.

FIG. 3 is a UV-visible spectrum measured in a range of from 190 nm to900 nm of the conductive polymer synthesized in Example 2 in an aqueoussolution.

FIG. 4 is a UV-visible spectrum measured in a range of from 190 nm to900 nm of the conductive polymer synthesized in Example 2 in a 0.2mole/liter aqueous ammonia solution.

FIG. 5 shows an IR spectrum of the conductive polymer (sulfonic acidgroup-free type) synthesized in Example 2.

FIG. 6 shows an IR spectrum of the conducting polymer (salt type)synthesized in Example 5.

FIG. 7 is a UV-visible spectrum measured in a range of from 190 nm to900 nm of the conductive polymer synthesized in Comparative Example 3(conventional method) in a 0.2 mole/liter aqueous ammonia solution.

FIG. 8 shows an IR spectrum of the conductive polymer synthesized inExample 13.

PREFERRED EMBODIMENTS OF THE INVENTION

The soluble aniline conducting polymer of the present invention containsas a repeating unit an alkoxyl group-substituted aminobenzenesulfonicacid, its alkali metal salt, ammonium salt and/or substituted ammoniumsalt, and it is a solid having a weight average molecular weight ofabout 1900 or more at room temperature.

Also, the soluble aniline conducting polymer of the present invention isa polymer containing a repeating unit represented by the formula (1),##STR2## wherein each of A¹, A², A³ and A⁴ is a group independentlyselected from the group consisting of hydrogen, an alkali metal, anammonium group and a substituted ammonium, R represents a C₁ -C₁₂straight-chain or branched alkyl group, x represents a number of from 0to 1, and n represents a polymerization degree which is a number of from3 to 5000, and it can also be expressed as a soluble aniline conductingpolymer which is a solid having a weight average molecular weight ofabout 1900 or more at room temperature. This polymer has a surfaceresistance not more than an order of 10⁸ Ω/□ (measured at a filmthickness of 0.1 μm), and exhibits excellent characteristics that itshows solubility to acidic solutions as described alter.

The alkali metal includes lithium, sodium, potassium, etc.

The substituted ammonium includes aliphatic ammoniums, cyclic saturatedammoniums, cyclic unsaturated ammoniums, etc.

The foregoing aliphatic ammoniums are represented by the followingformula, ##STR3## wherein each of R₂₁ to R₂₄ is a group independentlyselected from the group consisting of hydrogen, a C₁ -C₄ alkyl group,CH₂ OH and CH₂ CH₂ OH. For example, there are given methyl ammonium,dimethyl ammonium, trimethyl ammonium, ethyl ammonium, diethyl ammonium,triethyl ammonium, methylethyl ammonium, diethymethyl ammonium,dimethylethyl ammonium, propyl ammonium, dipropyl ammonium, isopropylammonium, diisopropyl ammonium, butyl ammonium, dibutyl ammonium,methylpropyl ammonium, ethylpropyl ammonium, methylisopropyl ammonium,ethylisopropyl ammonium, methylbutyl ammonium, ethylbutyl ammonium,tetramethyl ammonium, tetramethylol ammonium, tetraethyl ammonium,tetra-n-butyl ammonium, tetra-secbutyl ammonium, tetra-tert-butylammonium and the like. Of these ammoniums, those in which one of R₂₁ toR₂₄ is hydrogen, and other three are a C₁ -C₄ alkyl group are mostpreferred, and those in which two of R₂₁ to R₂₄ are hydrogen, and othertwo are a C₁ -C₄ alkyl group are preferred next to the former.

The cyclic saturated ammoniums include piperidinium, pyrrolidinium,morpholinium, piperazinium, derivatives having these skeletons, and thelike.

The cyclic unsaturated ammoniums include pyridinium, α-picolinium,β-picolinium, γ-picolinium, quinolinium, isoquinolinium, pyrrolinium,derivatives having these skeletons, and the like.

Examples of the foregoing R includes methyl, ethyl, propyl, isopropyl,n-butyl, sec-butyl, tertbutyl, hexyl, heptyl, octyl, nanonyl, decanyl,undecanyl and the like.

The foregoing x represents a number of from 0 to 1, and usually it is ina range of 0.2 to 0.8. Those having small x are obtained by oxidationwith an oxidizing agent such as benzoyl peroxide, ammoniumperoxodisulfate and hydrogen peroxide. Those having large x are obtainedby reduction with a reducing agent such as hydrazine, phenylhydrazine,sodium boron hydride, sodium hydride and the like.

Each of A¹ to A⁴ in the present invention is a group independentlyselected from the group consisting of hydrogen, an alkali metal,ammonium and a substituted ammonium. In other words, A¹ to A⁴ containedin the formula (1) may be the same or different.

Specifically, when polymerization is carried out in the presence ofsodium hydroxide, most of A¹ to A⁴ contained in the isolated polymer aresodium. However, when this polymer is treated with an acid solution, itcan be converted to a polymer in which most of A¹ to A⁴ have beensubstituted with hydrogen.

Similarly, polymerization in the presence of ammonia gives a polymer inwhich most of A¹ to A⁴ are ammonium; polymerization in the presence oftrimethylamine gives a polymer in which most of A¹ to A⁴ aretrimethylammonium; and polymerization in the presence of quinoline givesa polymer in which most of A¹ to A⁴ are quinolinium.

When basic compounds are used in mixture, A¹ to A⁴ are a mixture ofthese basic groups.

Specifically, when polymerization is carried out in the presence of bothsodium hydroxide and ammonia, A¹ to A⁴ in the isolated polymer are amixture of sodium and ammonium. When this polymer is treated with asolution containing sodium hydroxide and ammonia, A¹ to A⁴ in thetreated polymer, similarly to the above, are a mixture of sodium andammonium.

The soluble aniline conducting polymer of the present invention maycontain a monomer unit(s) as other repeating unit than the onerepresented by the above formula (1) so far as the solubility,conductivity and other properties of the polymer are not adverselyaffected. The above monomer unit is at least one member selected fromthe group consisting of a substituted or unsubstituted aniline,thiophene, pyrrole, phenylene, vinylene, other divalent unsaturatedgroups and divalent saturated groups. It is preferred that the solubleaniline conducting polymer of the present invention contains a repeatingunit of the formula (1) in an amount of 70% or more.

In the present invention, the solubility in alkaline water means that atleast 1 wt. % of the aniline conducting polymer can dissolve in a 0.1Naqueous ammonia without producing insoluble products. The solubility inacidic water means that at least 1 wt. % of the aniline conductingpolymer can dissolve in a 0.1M aqueous sulfuric acid solution withoutproducing insoluble products. The solubility in neutral water means thatat least 1 wt. % of the aniline conducting polymer can dissolve in wateritself without producing insoluble products. The solubility in organicsolvents means that at least 1 wt. % of the aniline conducting polymercan dissolve in a 0.1N ammoniacal alcohol solution without producinginsoluble products.

A method for producing the soluble aniline conducting polymer of thepresent invention comprises polymerizing at least one compound (1)selected from the group consisting of an acidic group-substitutedaniline, its alkali metal salt, an ammonium salt and a substitutedammonium salt with the aid of an oxidizing agent in a solutioncontaining a basic compound (2).

In the method for producing the solution aniline conducting polymer ofthe present invention, the foregoing acidic group-substituted aniline ispreferably represented by the formula (2), ##STR4## wherein each of R₁,R₂, R₃, R₄ and R₅ is selected from the group consisting of hydrogen, aC₁ -C₄ straight-chain or branched alkyl group, a C₁ -C₁₂ straight-chainor branched alkoxy group, an acidic group, a hydroxyl group, a nitrogroup and a halogen; at least one of R₁, R₂, R₃, R₄ and R5 represents anacidic group; and the acidic group referred to herein means a sulfonicacid group or a carboxyl group.

Among the compounds represented by the foregoing formula (2), those inwhich the acidic group has been bonded to the o- or m-position withrespect to the amino group give polymers which are more superior inperformance such as conductivity, solubility and the like.

The most representative examples of the above acidic group-substitutedaniline include a sulfonic acid group-substituted aniline and carboxylgroup-substituted aniline. Among these, the sulfonic acidgroup-substituted aniline is preferred since it tend to show a highconductivity as compared with the carboxyl group-substituted aniline.

The most representative examples of the sulfonic acid group-substitutedaniline include aminobenzenesulfonic acids. Specifically, o-, m- andp-aminobenzenesulfonic acids, aniline-2,6-disulfonic acid,aniline-2,5-disulfonic acid, aniline-3,5-disulfonic acid,aniline-2,4-disulfonic acid and aniline-3,4-disulfonic acid arepreferably used.

Other sulfonic acid group-substituted anilines include alkylgroup-substituted aminobenzenesulfonic acids such asmethylaminobenzenesulfonic acid, ethylaminobenzenesulfonic acid,n-propylaminobenzenesulfonic acid, isopropylaminobenzenesulfonic acid,n-butylaminobenzenesulfonic acid, sec-butylaminobenzenesulfonic acid,tert-butylaminobenzenesulfonic acid, etc.; hydroxyl group-substitutedaminobenzenesulfonic acids, nitro group-substituted aminobenzenesulfonicacids, halogen-substituted aminobenzenesulfonic acids such asfluoroaminobenzenesulfonic acid, chloroaminobenzenesulfonic acid,bromoaminobenzenesulfonic acid and the like. Among these, alkylgroup-substituted aminobenzenesulfonic acids and hydroxylgroup-substituted aminobenzenesulfonic acids are most preferred in termsof practical use. These sulfonic acid group-substituted anilines may beused alone or in a mixture of their isomers in any weight ratio.

The most representative examples of the carboxyl group-substitutedanilines include aminobenzenecarboxylic acids. Specifically, o-, m- andp-aminobenzenescarboxylic acids, aniline-2,6-dicarboxylic acid,aniline-2,5-dicarboxylic acid, aniline-3,5-dicarboxylic acid,aniline-2,4-dicarboxylic acid and aniline-3,4-dicarboxylic acid arepreferably used.

Other carboxyl group-substituted anilines include alkylgroup-substituted aminobenzenecarboxylic acids such asmethylaminobenzenecarboxylic acid, ethylaminobenzenecarboxylic acid,n-propylaminobenzenecarboxylic acid, isopropylaminobenzenecarboxylicacid, n-butylaminobenzenecarboxylic acid,sec-butylaminobenzenecarboxylic acid, tert-butylaminobenzenecarboxylicacid, etc.; hydroxyl group-substituted aminobenzenecarboxylic acids,nitro group-substituted aminobenzenecarboxylic acids,halogen-substituted aminobenzenecarboxylic acids such asfluoroaminobenzenecarboxylic acid, chloroaminobenzenecarboxylic acid,bromoaminobenzenecarboxylic acid and the like. Among these, alkylgroup-substituted aminobenzenecarboxylic acids and hydroxylgroup-substituted aminobenzenecarboxylic acids are most preferred interms of practical use. These carboxyl group-substituted anilines may beused alone or in a mixture of their isomers in any weight ratio.

Referring to specific examples of the acidic group-substituted anilinerepresented by the foregoing formula (2) in more detail, there are giventhe following:

sulfonic acid group-substituted alkylanilines,

carboxyl group-substituted alkylanilines,

sulfonic acid group-substituted hydroxyanilines,

carboxyl group-substituted hydroxyanilines,

sulfonic acid group-substituted nitroanilines,

carboxyl group-substituted nitroanilines,

sulfonic acid group-substituted fluoroanilines,

carboxyl group-substituted fluoroanilines,

sulfonic acid group-substituted chloroanilines,

carboxyl group-substituted chloroanilines,

sulfonic acid group-substituted bromoanilines and

carboxyl group-substituted bromoanilines.

Specific examples of the position and combination of these substituentswill be shown in Table 1.

                  TABLE 1                                                         ______________________________________                                        R.sub.1     R.sub.2                                                                             R.sub.3     R.sub.4                                                                           R.sub.5                                     ______________________________________                                        A           B     H           H   H                                           A           H     B           H   H                                           A           H     H           B   H                                           A           H     H           H   B                                           H           A     B           H   H                                           H           A     H           B   H                                           H           A     H           H   H                                           B           A     H           H   B                                           H           H     A           B   H                                           H           H     A           H   B                                           B           H     A           H   H                                           H           B     A           H   H                                           H           H     H           A   B                                           H           H     B           A   H                                           H           B     H           A   H                                           B           H     H           A   H                                           H           H     H           B   A                                           H           H     B           H   A                                           H           B     H           H   A                                           B           H     H           H   A                                           ______________________________________                                    

wherein

A represents one member selected from the group consisting of a sulfonicacid group, a carboxyl group, its alkali metal salt, ammonium salt andsubstituted ammonium salt.

B represents one member selected from the group consisting of an alkylgroup (e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,tert-butyl), a hydroxyl group, a nitro group and a halogen group (e.g.fluoro, chloro, bromo).

H represents hydrogen.

Further, referring to specific examples of the acidic group-substitutedaniline represented by the foregoing formula (2), there are givensulfonic acid group-substituted alkoxyanilines, that is, alkoxylgroup-substituted aminobenzenesulfonic acids represented by the formula(3), ##STR5## wherein R represents a C₁ -C₁₂, preferably C₁ -C₈, morepreferably C₁ -C₄ straight-chain or branched alkyl group.

Among the compounds represented by the foregoing formula (3), those inwhich the amino group has been bonded to the o- or m-position withrespect to the sulfonic acid group give polymers which are superior inperformance such as conductivity, solubility and the like.

The most representative examples of the foregoing alkoxylgroup-substituted aminobenzenesulfonic acid include aminoanisolesulfonicacids. Specifically, there are given 2-aminoanisole-3-sulfonic acid,2-aminoanisole-4-sulfonic acid, 2-aminoanisole-5-sulfonic acid,2-aminoanisole-6-sulfonic acid, 3-aminoanisole-2-sulfonic acid,3-aminoanisole-4-sulfonic acid, 3-aminoanisole-5-sulfonic acid,3-aminoanisole-6-sulfonic acid, 4-aminoanisole-2-sulfonic acid,4-aminoanisole-3-sulfonic acid and the like. Particularly,2-aminoanisole-3-sulfonic acid, 2-aminoanisole-4-sulfonic acid,2-aminoanisole-6-sulfonic acid, 3-aminoanisole-2-sulfonic acid,3-aminoanisole-4-sulfonic acid and 3-aminoanisole-5-sulfonic acid arepreferably used.

Other alkoxyl group-substituted aminobenzenesulfonic acids include2-amino-4-ethoxybenzenesulfonic acid, 3-amino-4-ethoxybenzenesulfonicacid, 2-amino-4-butoxybenzenesulfonic acid,3-amino-5-butoxybenzenesulfonic acid, 2-amino-4-propoxybenzenesulfonicacid, 3-amino-6-propoxybenzenesulfonic acid,2-amino-4-isobutoxybenzenesulfonic acid,3-amino-4-isobutoxybenzenesulfonic acid,3-amino-4-tert-butoxybenzenesulfonic acid,2-amino-4-tert-butoxybenzenesulfonic acid,2-amino-4-heptoxybenzenesulfonic acid, 3-amino-5-heptoxybenzenesulfonicacid, 2-amino-4-hexoxybenzenesulfonic acid,3-amino-5-octoxybenzenesulfonic acid, 2-amino-4-nanoxybenzenesulfonicacid, 3-amino-5-decanoxybenzenesulfonic acid,2-amino-4-undecanoxybenzenesulfonic acid,3-amino-5-dodecanoxybenzenesulfonic acid and the like.

These alkoxyl group-substituted aminobenzenesulfonic acids may be usedalone or in a mixture of their isomers in any weight ratio.

In the formulae (2) and (3), the alkali metals and substituted ammoniumsare as defined on the formula (1).

The basic compound (2) used in the present invention may be any compoundif it is a compound which forms a salt with the foregoing acidicgroup-substituted anilines. However, ammonia, aliphatic amines, cyclicsaturated amines, cyclic unsaturated amines, inorganic bases, etc. arepreferably used. Particularly, aliphatic amines, cyclic saturated aminesand cyclic unsaturated amines are preferred.

The aliphatic amines include a compound represented by the formula (6),##STR6## wherein each of R₂₇ to R₂₉ is a group independently selectedfrom the group consisting of a C₁ -C₄ alkyl group, CH₂ OH and CH₂ CH₂OH, and a hydroxide compound represented by the formula (7), ##STR7##wherein each of R₃₀ to R₃₃ is a group independently selected from thegroup consisting of hydrogen, a C₁ -C₄ alkyl group, CH₂ OH and CH₂ CH₂OH.

Those which are preferably used as the cyclic saturated amine includepiperidine, pyrrolidine, morpholine, piperazine, derivatives having theskeletons of these compounds, ammoniumhydroxide compounds of thesecompounds and derivatives, and the like.

Those which are preferably used as the cyclic unsaturated amine includepyridine, α-picoline, β-picoline, γ-picoline, quinoline, isoquinoline,pyrroline, derivatives having the skeletons of these compounds,ammoniumhydroxide compounds of these compounds and derivatives, and thelike.

Those which are preferably used as the inorganic base include metalhydroxides such as sodium hydroxide, potassium hydroxide, lithiumhydroxide and the like.

These basic compounds (2) are used in a concentration range of 0.1mole/liter or more, preferably 0.1 to 10.0 moles/liter, more preferably0.2 to 8.0 moles/liter. When the concentration is less than 0.1mole/liter, the yield of the resulting polymer lowers. When it is morethan 10.0 moles/liter, the conductivity of the resulting polymer tendsto lower.

The foregoing basic compounds (2) can be used in a mixture of any mixingratio.

The compound (1) (e.g. the above acidic group-substituted anilines) andthe basic compound (2) are used in a weight ratio of 1:100 to 100:1,preferably 10:90 to 90:10 of (1) to (2). When the proportion of thebasic compound is low, both the reactivity and conductivity lower. Onthe other hand, when it is high, the acidic group in the resultingpolymer and the basic compound tends to form a salt which decreases theconductivity.

The acidic group (3) in the compound (1) (e.g. the above acidicgroup-substituted anilines) and the basic compound (2) are used in amolar ratio of 1:100 to 100:1, preferably 1:0.25 to 1:20, morepreferably 1:0.5 to 1:15 of (3) to (2). When the proportion of the basiccompound is low, both the reactivity and conductivity lower. On theother hand, when it is high, the acidic group in the resulting polymerand the basic compound tends to form a salt which decreases theconductivity.

Polymerization or copolymerization is carried out by oxidationpolymerization with an oxidizing agent in a solution containing thebasic compound.

In this case, preferable examples of the solvent include water,methanol, ethanol, isopropanol, acetonitrile, methyl isobutyl ketone,methyl ethyl ketone, dimethylformamide, dimethylacetamide and the like.

The oxidizing agent is not critical so far as it has a standardelectrode potential of 0.6 V or more. Peroxodisulfuric acid, its saltssuch as ammonium peroxodisulfate, sodium peroxodisulfate, potassiumperoxodisulfate, etc. and hydrogen peroxide are preferably used. Thesecompounds are used in an amount of 0.1 to 5 moles, preferably 0.5 to 5moles based on 1 mole of the monomer. In this case, it is also effectiveto add a compound of a transition metal (e.g. iron, copper) as acatalyst.

The reaction is preferably carried out in a temperature range of -15° C.to 70° C. and more preferably -5° C. to 60° C. When the reactiontemperature is less than -15° C. or more than 70° C., the conductivityof the resulting polymer tends to lower.

Hydrogens in the sulfonic acid groups or carboxyl groups of the polymerproduced by the present invention may be replaced by one or more membersindependently selected from the group consisting of hydrogen, an alkalimetal, ammonium and a substituted ammonium. Therefore, there are caseswhere the selected members consist of a simple member or form a mixtureof different ones.

Specifically, when polymerization is carried out in the presence ofsodium hydroxide, hydrogens in the sulfonic acid groups or carboxylgroups of the isolated polymer are in the state where most of them havebeen replaced by sodium.

Similarly, when polymerization is carried out in the presence ofammonia, most of hydrogens in the sulfonic acid groups or carboxylgroups of the polymer are ammonium. In the case of polymerization in thepresence of trimethylamine, most of hydrogens are replaced bytrimethylammonium, and in the case of polymerization in the presence ofquinoline, most of the hydrogens are replaced by quinolinium.

When the basic compounds are used in a mixture, the hydrogens are in thestate where they have been mixed with the respective basic groups ofthese compounds.

Specifically, when polymerization is carried out in the presence ofsodium hydroxide and ammonia, hydrogens in the sulfonic acid groups orcarboxyl groups of the isolated polymer are in the state where they havebeen mixed with both sodium and ammonium. Similarly, when the polymerobtained above is treated with a solution containing both sodiumhydroxide and ammonia, hydrogens in the sulfonic acid groups or carboxylgroups of the polymer are in the state where they have been mixed withboth sodium and ammonium.

The polymer in which a part of the acidic groups described above hasformed a salt can be converted to a polymer in which the salt has beenreplaced by hydrogen, by treating the polymer in acidic solutions.

The acidic solution includes hydrochloric acid, sulfuric acid,p-toluenesulfonic acid, nitric acid and the like.

In the manufacturing method of the present invention, the resultingpolymer precipitates from the polymerization solvent, so that the degreeof formation of the salt is low. Therefore, a highly conductive,practical polymer can be produced without special need to treat thepolymer in the acidic solution.

The thus-obtained soluble aniline conducting polymer having sulfonicacid groups or carboxyl groups bonded to all the aromatic rings has apolymerization degree of 3 to 5000, preferably 5 to 5000, and a weightaverage molecular weight of about 1,900 to 3,240,000, preferably 3,200to 3,240,000, more preferably 20,000 to 3,240,000. Without applicationof additional sulfonation, this polymer can be dissolved in wateritself; water containing a base (e.g. ammonia, alkylamine) or a basicsalt (e.g. ammonium acetate, ammonium oxalate); water containing an acid(e.g. hydrochloric acid, sulfuric acid); an organic solvent (e.g. methylalcohol, ethyl alcohol, isopropyl alcohol); or a mixture thereof.

Referring to the solubility in detail, the soluble aniline conductingpolymer of the present invention dissolves in aqueous alkali solutions(e.g. 0.1 mole/liter aqueous ammonia) in an amount of 1 wt. % or more;in aqueous acidic solutions (e.g. 0.1 mole/liter aqueous sulfuric acidsolution) in an amount of 1 wt. % or more; in aqueous neutral solutions(e.g. water itself) in an amount of 1 wt. % or more; and in organicsolvents (e.g. 0.1 mole/liter ammoniacal alcohol solution) in an amountof 1 wt. % or more.

Any of the polymers and copolymers synthesized by the above method isconsidered to have a structure represented by the following formula (8):##STR8## wherein A is one member selected from the group consisting ofan acidic group (e.g. sulfonic acid group, carboxyl group), and itsalkali metal salt, ammonium salt and substituted ammonium salt; B is onemember selected from the group consisting of hydrogen, a C₁ -C₄straight-chain or branched alkyl group (e.g. methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, tert-butyl), a C₁ -C₁₂ straight-chain orbranched alkoxyl group, a hydroxyl group, a nitro group, and a halogengroup (e.g. fluoro, chloro, bromo); x represents a number of from 0 to1; and n represents a polymerization degree of from 3 to 5,000.

According to the process of the present invention, the resulting polymerusually has a value of x ranging from 0.2 to 0.8. However, when theoxidation is carried out with an oxidizing agent (e.g. benzoyl peroxide,ammonium peroxodisulfate, hydrogen peroxide), the resulting polymer hasa smaller value of x than the above. When the reduction is carried outwith a reducing agent (e.g. hydrazine, phenylhydrazine, sodium boronhydride, sodium hydride), the resulting polymer has a larger value of xthan the above.

As to the polymer of the present invention obtained with an alkoxylgroup-substituted aminobenzenesulfonic acid as a monomer and theconventional polymer, represented by the formulae (5) and (9),respectively, the outline of their solubility characteristics will beshown in Table 2.

                  TABLE 2                                                         ______________________________________                                        Present polymer                                                               (formula 5)        Conventional polymer                                       Alka-                      (formula 9)                                        line      Neutral  Acidic  Alkaline                                                                             Neutral                                                                              Acidic                               ______________________________________                                        SO.sub.3 H                                                                          o       o        o     o      o      x                                  type                                                                          SO.sub.3 M                                                                          o       o        o     o      x      x                                  type*                                                                         ______________________________________                                         o: Soluble                                                                    x: Insoluble                                                                  *: Means the form of sulfonic acid salt.                                 

The conductive composition of the present invention, an electricconductor produce from the same and methods for producing them will beillustrated below in detail.

Among the water-soluble aniline conducting polymers (a) constituting theabove conductive composition and electric conductor, preferred examplesare a soluble aniline conducting polymer of the present inventionrepresented by the foregoing structural formula (8), and a polymerderivative having 70% or more of the repeating unit of the formula (8),which is also of the present invention.

For the solvent (b), a component of the conductive composition, used inthe present invention, water or organic solvents are used. However,water or a mixed system of water and an organic solvent compatible withwater is preferred, and particularly, single use of water is morepreferred.

Specific examples of the organic solvent include alcohols (e.g.methanol, ethanol, propanol, isopropanol), ketones (e.g. acetone, methylisobutyl ketone), cellosolves (e.g. methyl cellosolve, ethylcellosolve), propylene glycols (e.g. methylpropylene glycol,ethylpropylene glycol), amides (e.g. dimethylformamide,dimethylacetamide), pyrrolidones (N-methylpyrrolidone,N-ethylpyrrolidone), hydroxyesters (e.g. ethyl lactate, methyl lactate,methyl β-methoxyisobutyrate, methyl α-hydroxyisobutyrate, ethylα-hydroxyisobutyrate, methyl α-methoxyisobutyrate) and the like. Amongthese, alcohols, propylene gylcols, amides and pyrrolidones arepreferably used, and alcohols are more preferably used. By using theabove organic solvents or solvents containing them, the coating propertyof the conductive composition onto substrates can be improved. Apreferred rate of the organic solvent used in the mixed system withwater is 1:100 to 100:1 of water to organic solvent.

When an acidic compound is added to the solvent (b), the conductivitycan be improved by joining of the doping effect of the acidic compound.The acidic compound includes inorganic acids (e.g. sulfuric acid,hydrochloric acid, nitric acid) and organic acids (e.g.p-toluenesulfonic acid, acetic acid, methanesulfonic acid). The rate ofweight of the acidic compound added to the solvent (b) is preferably70:30 to 100:0.01 of solvent to acidic compound.

Any of the solvents and acidic compounds described above can also beused in mixture of their respective two or more members in any weightratio.

In using the foregoing component (a) and solvent (b), the weight ratiois 0.1 to 20 parts by weight, preferably 0.5 to 15 parts by weight ofthe former (a) based on 100 parts by weight of the latter (b). When therate of the component (a) is less than 0.1 part by weight, theconductivity lowers. On the other hand, when it exceeds 20 parts byweight, the solubility, flatness and transparency become poor, and alsothe conductivity, which has already reached a peak, does not increasefurther more.

For the polymer compound (c), a component of the composition, used inthe present invention, water-soluble polymer compounds and polymercompounds which form emulsion in aqueous systems are used.

Specific examples of the water-soluble polymer compound includepolyvinyl alcohols (e.g. polyvinyl alcohol, polyvinyl formal, polyvinylbutyral), polyacrylamides [e.g. polyacrylamide,poly(N-tert-butylacrylamide), polyacrylamide methylpropanesulfonicacid], polyvinyl pyrrolidones, water-soluble alkyd resins, water-solublemelamine resins, water-soluble urea resins, water-soluble phenol resins,water-soluble epoxy resins, water-soluble polybutadiene resins,water-soluble acrylic resins, water-soluble urethane resins,water-soluble acryl/styrene copolymer resins, water-soluble vinylacetate/acryl copolymer resins, water-soluble polyester resins,water-soluble styrene/maleic acid copolymer resins, water-solublefluororesins and copolymers thereof.

Specific examples of the polymer compound which forms an emulsion inaqueous systems include aqueous alkyd resins, aqueous melamine resins,aqueous urea resins, aqueous phenol resins, aqueous epoxy resins,aqueous polybutadiene resins, aqueous acrylic resins, aqueous urethaneresins, aqueous acryl/styrene copolymer resins, aqueous vinyl acetateresins, aqueous vinyl acetate/acryl copolymer resins, aqueous polyesterresins, aqueous styrene/maleic acid copolymer resins, aqueousacryl/silica resins, aqueous fluororesins and copolymers thereof.

These high-molecular compounds may be used alone or in mixture of two ormore members in any weight ratio.

The rate of weight of the polymer compound (c) in the conductivecomposition is 0.1 to 400 parts by weight, preferably 0.5 to 300 partsby weight based on 100 parts by weight of the solvent (b). When the rateof weight is less than 0.1 part by weight, the film-forming property,moldability and strength become poor. On the other hand, when it exceeds400 parts by weight, the water-soluble aniline conducting polymer (a)lowers in solubility and becomes poor in conductivity.

The transparent conductive polymer film in the electric conductor can beformed by single use of the water-soluble aniline conducting polymer(a). However, by incorporating the foregoing polymer compound (c) intothe above polymer (a), the hardness, abrasion resistance andadhesion-to-substrate of the film can be improved.

The weight ratio of the water-soluble aniline conducting polymer (a) andpolymer compound (c) is 0.025:100 to 100:0.5, preferably 0.15:100 to100:1 of (a) to (c).

When the rate of weight of the polymer (a) is outside the above range,the conductivity lowers, and flatness and transparency become poor.

When the rate of weight of the compound (c) is outside the above range,the hardness, abrasion resistance and conductivity of the film lower,and the adhesion-to-substrate of the film becomes poor.

For the nitrogen-containing compound (d), a component of thecomposition, used in the present invention, the compounds represented bythe formulae (9) and (10) are used. The structural formula of aminesused is shown by the formula (9), ##STR9## wherein each of R₂₀ to R₂₂independently represents hydrogen, a C₁ -C₄ alkyl group, CH₂ OH, CH₂ CH₂OH, CONH₂ or NH₂. The structural formula of quaternary ammonium salts isshown by the formula (10), ##STR10## wherein each of R₂₃ to R₂₆independently represents hydrogen, a C₁ -C₄ alkyl group, CH₂ OH, CH₂ CH₂OH, CONH₂ or NH₂ ; and X⁻ represents OH⁻, 1/2 SO₄ ²⁻, NO₃ ⁻, 1/2 CO₃ ²⁻,HCO₃ ⁻, 1/2 (COO)₂ ²⁻ or R¹ COO-- in which R¹ is a C₁ -C₃ alkyl group.

In using the above nitrogen-containing compounds (d), the conductivitycan be further improved by using these amines and ammonium salts inmixture. Specifically, there are given the following combinations: NH₃/(NH₄)₂ CO₃, NH₃ /(NH₄)HCO₃, NH₃ /(NH₄)HCO₃, NH₃ /CH₃ COONH₄, NH₃/(NH₄)₂ SO₄, N(CH₃)₃ /(NH₄)HCO₃, N(CH₃)₃ /CH₃ COONH₄, N(CH₃)/₃ (NH₄)₂SO₄ and the like. Any mixing ratio of these compounds may be used, butthe ratio of 1:10 to 10:0 of the amines to ammonium salts is preferred.

The rate of weight of the nitrogen-containing compound (d), a componentof the composition, is 0 to 30 parts by weight, preferably 0 to 20 partsby weight based on 100 parts by weight of the component (b). When therate of weight exceeds 20 parts by weight, the solution shows a strongbasicity to result in lowering in the conductivity. The pH of thesolution can optionally be adjusted by changing the concentration, kindand mixing ratio of the nitrogen-containing compound, and a pH range of0.1 to 12 can be used.

The conductive composition of the present invention can form a filmhaving good performances by using the mixtures of the components (a) and(b), (a), (b) and (c), or (a), (b), (c) and (d). However, when a surfaceactive agent (e) is further added to the above respective conductivecompositions, the flatness, coating property and conductivity arefurther improved.

The surface active agent (e) include anionic surface active agents,cationic surface active agents, amphoteric surface active agents,nonionic surface active agents and fluorine-containing surface activeagents.

The anionic surface active agents include alkylsulfonic acid,alkylbenzenesulfonic acid, alkylcarboxylic acid,alkylnaphthalenesulfonic acid, α-olefinsulfonic acid,dialkylsulfosuccinic acid, α-sulfonated fatty acid,N-methyl-N-oleyltaurine, petroleumsulfonic acid, alkyl sulfate,sulfurized oil and fat, polyoxyethylene alkyl ether sulfuric acid,polyoxyethylene styrenated phenyl ether sulfuric acid, alkylphosphoricacid, polyoxyethylene alkyl ether phosphoric acid, polyoxyethylenealkylphenyl ether phosphoric acid, naphthalenesulfonic acid/formaldehydecondensates, the salts of these compounds and the like.

The cationic surface active agents include primary to tertiary aliphaticamines, quaternary ammonium, tetraalkylammonium, trialkylbenzylammonium,alkylpyridinium, 2-alkyl-1-alkyl-1-hydroxyethylimidazolinium,N,N-dialkylmorpholinium, poyethylenepolyamine fatty acid amide,polyethylenepolyamine fatty acid amide/urea condensates, theirquaternary ammoniums and the salts of these compounds and the like.

The amphoteric surface active agents include betaines such asN,N-dimethyl-N-alkyl-N-carboxymethylammonium betaine,N,N,N-trialkyl-N-sulfoalkyleneammonium betaine,N,N-dialkyl-N,N-bispolyoxyethyleneammonium sulfuric acid ester betaine,2-alkyl-1-carboxymethyl-1-hydroxyethylimidazolinium betaine, etc.;aminocarboxylic acids such as N,N-dialkylaminoalkylenecarboxylic acidsalt, etc.; and the like.

The nonionic surface active agents include polyoxyethylene alkyl ether,polyoxyethylene alkylphenyl ether, polyoxyethylene polystyrylphenylether, polyoxyethylene-polyoxypropylene glycol,polyoxyethylene-polyoxypropylene alkyl ether, polyhydric alcohol/fattyacid partial ester, polyoxyethylene/polyhydric alcohol/fatty acidpartial ester, polyoxyethylene fatty acid ester, polyglycerin fatty acidester, polyoxyethylenated castor oil, fatty acid diethanol amide,polyoxyethylene alkylamine, triethanolamine/fatty acid partial ester,trialkylamine oxide, and the like.

The fluorine-containing surface active agents includefluoroalkylcarboxylic acid, perfluoroalkylcarboxylic acid,perfluoroalkylbenzenesulfonic acid, perfluoroalkylpolyoxyethyleneethanol and the like. Here, the alkyl groups used are those havingpreferably 1 to 24 carbon atoms, more preferably 3 to 18 carbon atoms.The above surface active agents may be used in mixture of two or more ofthem.

In the present invention, when the conductive composition contains thecomponent (c), the nonionic surface active agents are particularlypreferably used among the surface active agents described above.Further, among the nonionic surface active agents, polyoxyethylenesrepresented by the formula (11) are preferably used;

    HO(CH.sub.2 CH.sub.2 O).sub.n R                            (11)

wherein R represents a C₁ -C₂₄ straight-chain or branched alkyl group ora C₁ -C₂₄ straight-chain or branched alkylsubstituted phenyl group, andn represents the number of oxyethylene groups which are a repeatingunit, the number being 1 to 100.

Of the polyoxyethylenes, polyoxyethylene alkyl ether and polyoxyethylenealkylphenyl ether are preferably used, and particularly, polyoxyethylenealkylphenyl ether is preferably used.

The number, n, of the oxyethylene units, which are a repeating unit, ispreferably 5 to 100, more preferably 10 to 100.

When the conductive composition contains no component (c), the anionicsurface active agents are particularly preferably used among the surfaceactive agents described above. Among the anionic surface active agents,those having a sulfonic acid group, a carboxyl group or the like as ananionic group in the molecule are further preferably used.

The surface active agents may be used in mixture of two or more of them.

The rate of weight of the component (e) is 0 to 10 parts by weight,preferably 0 to 5 parts by weight based on 100 parts by weight of thesolvent (b). When the rate of weight exceeds 10 parts by weight, thereappear such phenomena that the coating property improves, but theflatness lowers, or that the flatness improves, but the conductivitybecomes inferior.

The conductive composition of the present invention is prepared byadding to the solvent (b) either one of the following combinations (1),(2), (3) or (4);

(1) the water-soluble aniline conducting polymer (a) alone,

(2) (a) and a polymer compound (c),

(3) (a), (c) and a nitrogen-containing compound (d), and

(4) a surface active agent (e) and either one of (1), (2) or (3), andstirring the mixture at room temperature or with heating to dissolve ormix the components completely. When solid matters precipitate at roomtemperature, the solution is used after filtration. The electricconductor of the present invention can be formed by coating theconductive composition prepared as described above onto a substrate.When these components are mixed, blade-type stirring-kneading apparatussuch as spiral mixers, planetary mixers, dispersers, hybrid mixers, etc.are preferably used. After mixing, it is desirable to carry outdispersion or dissolution thoroughly using ball-type kneading apparatussuch as ball mills, vibration mills, sand mills, roll mills and thelike.

The conductive composition used to form the electric conductor of thepresent invention is applied to the surface of a substrate by methodsused for common paints. For example, the methods include coating methodssuch as cast coating, screen coating, etc. with gravure coaters, rollcoaters, curtain flow coaters, spin coaters, bar coaters, reverse rollcoaters, kiss coaters, fountain coaters, rod coaters, air doctorcoaters, knife coaters, blade coaters, etc.; spraying methods such asspray coating, etc.; dipping methods such as dipping, and the like.

It is possible for the transparent conducting polymer film formed withthe conductive composition to have a thickness of 0.01 to 1000 μm.However, when the film is thick, the transparent conducting polymer filmlowers in the transparency. Accordingly, as thin a film as possible isrequired. The film thickness is preferably in a range of from 0.01 to500 μm, more preferably from 0.02 to 100 μm.

In order to obtain the transparent conducting polymer film having theabove thickness, it is desirable that the viscosity of the conductivecomposition is in a range of 100 cp or less, preferably from 1 to 500cp, and the solid content of the composition is in a range of 0.1 to 80wt. %.

After the transparent conducting polymer film is formed on thesubstrate, it may be merely allowed to stand at room temperature asaftertreatment. It is however preferred to apply heat-treatment asafter-treatment because the amounts of the residual components (b) and(d) can be more reduced by heating, which makes the conductivity better,i.e. the value of resistance smaller. Although the amount of thecomponent (d) remaining in the electric conductor depends upon the usesof the electric conductor, it is desirable to make the above amount 2parts by weight or less, preferably 1 part by weight or less based on100 parts by weight of the conductive film. Further, it is better forthe component (b) not to exist substantially. A preferred heat-treatmentis heating at 250° C. or less, preferably in a range of 40° C. to 200°C. When the temperature is higher than 250° C., deterioration of thecomponent (a) sometimes causes decrease in conductivity.

As the substrate to be coated with the conductive composition, there areused polymer compounds, woods, papers, ceramics and ceramics films, orglass plates, etc. For example, the polymer compounds and their filmsinclude polyethylene, polyvinyl chloride, polypropylene, polystyrene,polyester, ABS resin, AS resin, methacrylic resin, polybutadiene,polycarbonate, polyarylate, polyvinylidenefluoride, polyamide,polyimide, polyaramide, polyphenylene sulfide, polyetheretherketone,polyphenylene ether, polyethernitrile, polyamideimide, polyethersulfone, polysulfone, polyetherimide, polybutyrene terephthalate andtheir films. These polymer films are used to form a transparentconducting polymer film on at least one surface of them. Therefore, inorder to improve the adhesion-to-film of the conductive high-molecularfilm, it is desirable to apply corona surface treatment or plasmatreatment to the surface of these high-molecular films.

The polyaniline polymer of the present invention shows both a highconductivity and an excellent solubility in organic solvents (e.g.alcohols) and aqueous solutions having all pHs ranging over thealkaline, neutral (particularly water itself) and acidic regions,because the polymer has sulfonic acid groups and alkoxyl groups bondedto all of its benzene nuclei.

The conductive composition of the present invention makes it possible touse, as a solvent for it, aqueous solutions having all pHs ranging overthe alkaline, neutral (particularly water itself) and acidic regions,because the conductive component, i.e. the water-soluble aniline seriesconductive polymer, contained in the composition has sulfonic acidgroups and alkoxyl groups bonded to all of the nuclei of the component.Therefore, by merely applying the composition to suitable substrates bycoating, spraying, casting or dipping and then heat-treatment, there canbe obtained a conductive thin film which develops a humiditydependence-free, high conductivity and is excellent in film-formingproperty, moldability and transparency.

In the present invention, the electric conductor which develops ahumidity dependence-free, high conductivity and has only a smalldispersion of surface resistance can be obtained by forming atransparent conductive film comprising the water-soluble anilineconducting polymer or the same polymer and the polymer compound andhaving excellent film-forming property, moldability and transparency onsuitable substrates by processing such as coating, spraying, casting,dipping, etc. and then merely allowing the formed film to stand at roomtemperature or applying heat-treatment to the film.

The present invention could develop a novel polymerization method whichbreaks the conventional fixed idea that anilines having an acidic group(e.g. sulfonic acid group, carboxyl group) are difficult to undergochemical oxidation polymerization by themselves. Thus, by causing all ofthe benzene nuclei to have a sulfonic acid or carboxyl group, thepresent invention could provide a method for producing a novelpolyaniline polymer of high molecular weight having both a highconductivity and an excellent solubility to organic solvents (e.g.alcohols) and aqueous solutions having all pHs ranging over thealkaline, neutral (particularly water itself) and acidic regions.

The resulting polymer could form a film of practical value because ithas a high molecular weight as compared with the polymer of acidicgroup-substituted anilines obtained by the conventional methods.

The present invention will be illustrated in more detail with referenceto the following examples, but it is not to be interpreted as beinglimited to these examples.

IR spectrum was measured with Model 1600 produced by Perkin Elmer Co.,and UV visible spectrum was measured with UV-3100 produced by ShimadzuSeisakusho, Ltd.

Measurement of molecular weight distribution and molecular weight(converted to polystyrene basis) was carried out by measurement of GPCwith a GPC column for N,N-dimethylformamide. As to the column, threekinds of column for N,N-dimethylformamide were used in connection. Forthe eluting solution, an N,N-dimethylformamide solution containing 10mM/liter of triethylamine and 100 mM/liter of lithium bromide was used.Measurement of conductivity (%) was carried out by the four-terminalmethod, and that of surface resistance was carried out by thetwo-terminal method.

EXAMPLE 1

One hundred milimoles of 2-aminoanisole-4-sulfonic acid was dissolved ina 4 moles/liter aqueous ammonia solution at 25° C. with stirring, and anaqueous solution containing 100 mmoles of ammonium peroxodisulfate wasadded dropwise thereto. After finish of addition, the reaction solutionwas further stirred at 25° C. for 12 hours. The reaction product wasfiltered off, washed and dried to obtain 15 g of a polymer powder.

This polymer had a volume resistance of 9.0 Ωcm. The result of molecularweight measurement showed number average molecular weight, 200,000;weight average molecular weight, 330,000; Z average molecular weight,383,000; dispersion degree, MW/MN, 1.64 and MZ/MW, 1.16.

FIG. 1 is a chart in the measurement of molecular weight of theconducting polymer synthesized in Example 1.

The polymer was added little by little to each of 10 ml of water, 10 mlof a 0.1 mole/liter aqueous sulfuric acid solution and 10 ml of a 0.1mole/liter aqueous ammonia. At a time when more polymer became to failto dissolve, each solution was filtered, and the amount dissolved wasmeasured to find that the solubility of the conducting polymersynthesized in Example 1 was as follows:

    ______________________________________                                        water                    210 mg/ml                                            0.1 mole/liter aqueous sulfuric                                                                        205 mg/ml                                            acid solution                                                                 0.1 mole/liter aqueous ammonia                                                                         190 mg/ml.                                           ______________________________________                                    

Three parts by weight of the above polymer was dissolved in 100 parts byweight of a 0.2 mole/liter aqueous sulfuric acid solution at roomtemperature with stirring to prepare a conductive composition (solvent:aqueous sulfuric acid solution).

The solution thus obtained [type: (a)+(b)] was coated onto a glasssubstrate by the spin coating method and dried at 100° C. A film havinga thickness of 0.1 μm, a smooth surface and a surface of 3.5×10⁶ Ω/□,was obtained.

EXAMPLE 2

One hundred milimoles of 2-aminoanisole-4-sulfonic acid was dissolved ina 4 moles/liter aqueous trimethylamine solution at 4° C. with stirring,and an aqueous solution containing 100 mmoles of ammoniumperoxodisulfate was added dropwise thereto. After finish of addition,the reaction solution was further stirred at 25° C. for 6 hours. Thereaction product was filtered off, washed and dried to obtain 12 g of apolymer powder.

This polymer was added to an acetone solution containing 1 mole/liter ofPTS, and after stirring for 1 hour, the reaction product was filteredoff, washed and dried to obtain 10 g of the powder of a sulfonic acidgroup-free polymer.

This polymer had a volume resistance of 5.5 Ωm.

FIG. 2 is the UV visible spectrum from 190 nm to 900 nm of theconducting polymer synthesized in Example 2 in a 0.1 mole/liter aqueoussulfuric acid solution. FIG. 3 is the UV visible spectrum from 190 nm to900 nm of the conducting polymer synthesized in Example 2 in an aqueoussolution. FIG. 4 is the UV visible spectrum from 190 nm to 900 nm of theconducting polymer synthesized in Example 2 in a 0.2 mole/liter aqueousammonia solution. FIG. 5 shows the IR spectrum of the conducting polymer(sulfonic acid group-free type) synthesized in Example 2.

The assignment of the IR spectrum is as follows:

sulfonic acid group: absorption in the vicinity of 1120, 1020 cm⁻¹

ammonium salt of sulfonic acid group: absorption in the vicinity of 1400cm⁻¹.

skeleton of polymer: absorption in the vicinity of 1500 cm⁻¹.

One part by weight of the above polymer was dissolved in 100 parts byweight of water at room temperature with stirring to prepare aconductive composition. Since the pH of the composition was about 3.5,it is presumed that about 80% or more of the sulfonic acid groups in thepolymer is in a free state.

The solution thus obtained (solvent: water itself) [type, (a)+(b)] wascoated onto a glass substrate by the casting method and dried at 100° C.A film having a thickness of 0.1 μm, a smooth surface and a surfaceresistance of 6.0×10⁷ Ω/□, was obtained.

0.05 Part by weight of PTS (p-toluenesulfonic acid), an acidic compound,was dissolved in the above conductive composition with stirring toprepare a conductive composition.

The solution thus obtained (solvent: aqueous acidic solution) was coatedonto a PET film by the casting method and dried at 70° C. A film havinga thickness of 0.5 μm, a smooth surface and a surface resistance of1.0×10⁷ Ω/□, was obtained.

EXAMPLE 3

One hundred milimoles of 2-aminoanisole-4-sulfonic acid was dissolved ina 4 moles/liter aqueous quinoline solution at 4° C. with stirring, andan aqueous solution containing 100 mmoles of ammonium peroxodisulfatewas added dropwise thereto. After finish of addition, the reactionsolution was further stirred at 25° C. for 12 hours. The reactionproduct was filtered off, washed and dried to obtain 16 g of a polymerpowder.

This polymer had a volume resistance of 11.0 Ωcm.

Three parts by weight of the above polymer and 30 parts by weight of aurethane resin which forms emulsion in an aqueous system(ADEKABONTITER-232 produced by Asahi Denka Kogyo Co., Ltd.) weredissolved in 100 parts by weight of water at room temperature withstirring to prepare a conductive composition. Since the pH of thiscomposition was about 6.0, it is presumed that about 20% or more of thesulfonic acid groups in the polymer forms a salt (solvent: wateritself).

The solution thus obtained was coated onto a PET film by the spincoating method and dried at 8° C. A film having a thickness of 0.1 μm, asmooth surface and a surface resistance of 6.0×10⁶ Ω/□, was obtained.

The solution thus obtained [type: (a)+(b)+(c)] was coated onto a PETfilm by the spin coating method and dried at 80° C. A film having athickness of 0.1 Ωm, a smooth surface and a surface resistance of1.5×10⁶ Ω/□, was obtained.

EXAMPLE 4

One hundred milimoles of 3-amino-4-ethoxybenzenesulfonic acid wasdissolved in a 3 moles/liter aqueous 2-methylpyridine (α-picoline)solution at 25° C. with stirring. Thereafter, an aqueous solutioncontaining 100 mmoles of ammonium peroxodisulfate was added dropwisethereto. After finish of addition, the reaction solution was furtherstirred at 25° C. for 12 hours. The reaction product was filtered off,washed and dried to obtain 14 g of a polymer powder.

This polymer had a volume resistance of 8.4 Ωcm.

Three parts by weight of the above polymer was dissolved in 100 parts byweight of water/isopropanol (7/3) at room temperature with stirring toprepare a conductive composition.

The solution thus obtained was coated onto a glass substrate by the spincoating method and dried at 120° C. A film having a thickness of 0.1 μm,a smooth surface and a surface resistance of 4.5×10⁶ Ω/□, was obtained.

Three parts by weight of the above polymer, 20 parts by weight of anacryl/styrene resin which forms emulsion in an aqueous system (NICASOLRX-832A produced by Nihon Carbide Kogyo Co., Ltd.) and 1.0 part byweight of ammonia were dissolved in 100 parts by weight ofwater/isopropyl alcohol (7/3) at room temperature with stirring toprepare a conductive composition (solvent: alkaline aqueous alcoholsolution).

The solution thus obtained [type: (a)+(b)+(c)+(d)] was coated onto aglass substrate by the spin coating method and dried at 120° C. Theamount of the component (d) remaining in the formed film was 1% or lessbased on the weight of the film. A film having a thickness of 0.4 μm, asmooth surface and a surface resistance of 5.0×10⁶ Ω/□, was obtained.

EXAMPLE 5

One hundred milimoles of 2-aminoanisole-4-sulfonic acid was dissolved ina 4 moles/liter aqueous triethanolamine solution at 10° C. withstirring, and an aqueous solution containing 100 mmoles of ammoniumperoxodisulfate was added dropwise thereto. After finish of addition,the reaction solution was further stirred at 25° C. for 12 hours. Thereaction product was filtered off, washed and dried to obtain 12 g of apolymer powder.

This polymer had a volume resistance of 12 Ωcm.

FIG. 6 shows the IR spectrum of the conductive polymer (salt type)synthesized in Example 5.

Three parts by weight of the above polymer and 100 parts by weight of awater-soluble polyester resin (ARASTAR 300 produced by Arakawa KagakuKogyo Co., Ltd.) were dissolved in 100 parts by weight of water at roomtemperature with stirring to prepare a conductive composition.

The solution thus obtained was coated onto a PET film by means of agravure coater having a depth of 35 μm and dried at 70° C. A film havinga thickness of 0.5 μm, a smooth surface and a surface resistance of4.5×10⁶ Ω/□, was obtained.

Three parts by weight of the above polymer and 80 parts by weight of awater-soluble polyester resin (ARASTAR 300 produced by Arakawa KagakuKogyo Co., ltd.) were dissolved in 100 parts by weight of water at roomtemperature with stirring to prepare a conductive composition (solvent,water itself).

The solution thus obtained [type: (a)+(b)+(c)] was coated onto a PETfilm by the casting method and dried at 70° C. A film having a thicknessof 0.5 μm, a smooth surface and a surface resistance of 6.5×10⁶ Ω/□, wasobtained.

0.05 Part by weight of polyoxyethylene nonylphenyl ether was dissolvedin the above conductive composition with stirring to prepare aconductive composition.

The solution thus obtained [type: (a)+(b) +(c)+(d)] was coated onto aPET film by the casting method and dried at 70° C. A film having athickness of 0.5 μm, a smooth surface and a surface resistance of3.5×10⁶ Ω/□, was obtained.

EXAMPLE 6

One hundred milimoles of 2-aminoanisole-4-sulfonic acid was dissolved ina 4 moles/liter aqueous piperidine solution at 25° C. with stirring, andan aqueous solution containing 100 mmoles of ammonium peroxodisulfatewas added dropwise thereto. After finish of addition, the reactionsolution was further stirred at 25° C. for 12 hours. The reactionproduct was filtered off, washed and dried to obtain 15 g of a polymerpowder.

This polymer had a volume resistance of 18 Ωcm.

Two parts by weight of the above polymer was dissolved in 100 parts byweight of a 0.2 mole/liter aqueous ammonia at room temperature withstirring to prepare a conductive composition.

The solution thus obtained was coated onto a PET film by the spincoating method and dried at 80° C. A film having a thickness of 0.1 μm,a smooth surface and a surface resistance of 4.0×10⁷ Ω/□, was obtained.

Two parts by weight of the above polymer and 50 parts by weight of anacrylic resin which forms emulsion in an aqueous system (SAIBINOLEK-1005 produced by Saiden Kagaku Co., Ltd.) were dissolved in 100 partsby weight of water at room temperature with stirring with a high-speeddisperser, treated with a sand mill and then filtered through a filterpaper (Whatman's filter No. 3) to obtain a conductive composition havinga viscosity of 13 cp. The viscosity was measured with a Ubbelohdeviscometer (solvent; water itself).

The solution thus obtained [type: (a)+(b)+(c)] was coated onto the wholesurface of a polyester film of 75 μm in thickness (LUMIRAR T typeproduced by Toray Industries, Inc.) by means of a gravure coater havinga depth of 35 μm to form a transparent conducting polymer film having adry film thickness of 0.4 μm. The resulting film was heat-aged (60° C.,72 hours), and its surface resistance was measured to find that thedispersion of the surface resistance was small as described below:average value, 2.5×10⁶ Ω/□; maximum value, 2.7×10⁶ Ω/□; and minimumvalue, 2.2×10⁶ Ω/□. The above polymer film had a light transmittance of90% or more, and a haze of 15 or less.

This film was held for 120 hours in a high-temperature, high-humidityatmosphere of 60° C.×95% RH, and its surface resistance was measured tofind that it was 3.2×10⁶ Ω/□, showing that the conductivity wasmaintained.

EXAMPLE 7

One hundred milimoles of 3-amino-4-ethoxy-benzenesulfonic acid wasdissolved in a 3 moles/liter aqueous sodium hydroxide solution at 4° C.with stirring, and an aqueous solution containing 100 mmoles of ammoniumperoxodisulfate was added dropwise thereto. After finish of addition,the reaction solution was further stirred at 25° C. for 6 hours. Thereaction product was filtered off, washed and dried to obtain 15 g of apolymer powder.

This compound had a volume resistance of 20 Ωcm. This polymer was addedto an acetone solution containing 1 mole/liter of PTS, and afterstirring for 1 hour, the reaction product was filtered off, washed anddried to obtain 10 g of the powder of a sulfonic acid group-freepolymer.

Three parts by weight of the above polymer was dissolved in 100 parts byweight of water at room temperature with stirring to prepare aconductive composition. This composition had a viscosity of 2.75 cp (at25° C.). This viscosity was measured with a Ubbelohde viscometer.

Since the pH of the composition was about 3.8, it is presumed that about80% or more of the sulfonic acid groups in the polymer was in a freestate.

The solution thus obtained was coated onto a glass substrate by the spincoating method and dried at 80° C. A film having a thickness of 0.1 μm,a smooth surface and a surface resistance of 8.0×10⁷ Ω/□, was obtained.

Three parts by weight of the above polymer and 0.05 part by weight ofdodecylbenzenesulfonic acid were dissolved in 100 parts by weight ofwater at room temperature with stirring to prepare a conductivecomposition. This composition had a viscosity of 2.55 cp (25° C.). Thisviscosity was measured with a Ubbelohde viscometer (solvent; aqueousacidic solution containing an organic acid).

Since the pH of this composition was about 3.2, it is presumed thatabout 80% or more of the sulfonic acids in the polymer was in a freestate.

The solution thus obtained [type: (a)+(b)+(e)] was coated onto a glasssubstrate by the spin coating method and dried at 80° C. A film having athickness of 0.1 μm, a smooth surface and a surface resistance of6.0×10⁶ Ω/□, was obtained.

EXAMPLE 8

One hundred milimoles of 2-aminoanisole-4-sulfonic acid was dissolved in3 moles/liter aqueous triethylamine solution at 4° C. with stirring, andan aqueous solution containing 100 mmoles of ammonium peroxodisulfatewas added dropwise thereto. After finish of addition, the reactionsolution was further stirred at 25° C. for 6 hours. The reaction productwas filtered off, washed and dried to obtain 14 g of a polymer powder.

This polymer had a volume resistance of 20 Ωcm.

Three parts by weight of the above polymer and 10 parts by weight ofpolyvinyl alcohol (produced by Denki Kagaku Kogyo Co., Ltd.) weredissolved in 100 parts by weight of water at room temperature withstirring to prepare a conductive composition (solvent; water itself).

The solution thus obtained [type: (a)+(b)+(c)] was coated onto a glasssubstrate by the spin coating method and dried at 80° C. A film having athickness of 0.1 μm, a smooth surface and a surface resistance of3.0×10⁶ Ω/□, was obtained.

EXAMPLE 9

Three parts by weight of the polymer synthesized in Example 8 and 0.5part by weight of triethylamine were dissolved in 100 parts by weight ofisopropyl alcohol at room temperature with stirring to prepare aconductive composition (solvent: organic solvent only).

The solution thus obtained [type: (a)+(b)+(d)] was coated onto a PETfilm by the spin coating method and dried at 100° C. A film having athickness of 0.1 μm, a smooth surface and a surface resistance of5.0×10⁶ Ω/□, was obtained.

EXAMPLE 10

Three parts by weight of the polymer synthesized Example 1, 0.5 part byweight of ammonia and sodium alkylnaphthalenesulfonate (PEREX NBproduced by Kao Soap Co., Ltd.) were dissolved in 100 parts by weight ofwater at room temperature with stirring to prepare a conductivecomposition.

The solution thus obtained [type: (a)+(b)+(d)+(e)] was coated onto aglass substrate by the spin coating method and dried at 100° C. A filmhaving a thickness of 0.1 μm, a smooth surface and a surface resistanceof 3.9×10⁶ Ω/□, was obtained.

EXAMPLE 11

Three parts by weight of the polymer synthesized in Example 2, 80 partsby weight of a polyester resin which forms emulsion in an aqueous system(AY241W produced by Hoechst Japan Co., Ltd.) and 0.5 part by weight ofammonia were dissolved in 100 parts by weight of water at roomtemperature with stirring to prepare a conductive composition.

The solution thus obtained [type: (a)+(b)+(c)+(d)] was coated onto aglass substrate by the spin coating method and dried at 100° C. A filmhaving a thickness of 0.1 μm, a smooth surface and a surface resistanceof 6.0×10⁶ Ω/□, was obtained.

EXAMPLE 12

Three parts by weight of the polymer synthesized in Example 2, 80 partsby weight of a polyester resin which forms emulsion in an aqueous system(AY241W produced by Hoechst Japan Co., Ltd.), 0.5 part by weight ofammonia and 0.1 part by weight of polyoxyethylene-p-oleyl ether weredissolved in 100 parts by weight of water at room temperature withstirring to prepare a conductive composition.

The solution thus obtained [type: (a)+(b)+(c)+(d)+(e)] was coated onto aglass substrate by the spin coating method and dried at 100° C. A filmhaving a thickness of 0.1 μm, a smooth surface and a surface resistanceof 3.5×10⁶ Ω/□, was obtained.

Comparative Example 1

One hundred milimoles of 2-aminoanisole-4-sulfonic acid was suspended inwater at 4° C. with stirring, and an aqueous solution containing 100mmoles of ammonium peroxodisulfate was added dropwise thereto. Afterfinish of addition, the reaction solution was further stirred at 25° C.for 12 hours. Thereafter, the reaction solution was vacuum-distilled,and the concentrated product was isolated, washed and dried to obtain 6g of a polymer powder. This polymer had a volume resistance of >10.sup.Ωcm.

Three parts by weight of the above polymer was dissolved in 100 parts byweight of water at room temperature with stirring to prepare aconductive composition.

The solution thus obtained was coated onto a PET film by the spincoating method and dried at 80° C. A film having a thickness of 0.1 μm,a poor film-forming property and a surface resistance of 6.0×10¹² Ω/□ ormore, was obtained.

Comparative Example 2

One hundred milimoles of 2-aminoanisole-4-sulfonic acid was suspended ina 1 mole/liter aqueous sulfuric acid solution at 25° C. with stirring,and a 1 mole/liter aqueous sulfuric acid solution containing 100 mmolesof ammonium peroxodisulfate was added dropwise thereto. After finish ofaddition, the reaction solution was further stirred at 25° C. for 12hours. Thereafter, the reaction solution was vacuum-distilled, and theconcentrated product was isolated, washed and dried to obtain 3 g of apolymer powder. This polymer had a volume resistance of >10⁶ Ωcm.

Three parts by weight of the above polymer was dissolved in 100 parts byweight of water at room temperature with stirring to prepare aconductive composition.

The solution thus obtained was coated onto a glass substrate by the spincoating method, but a film was not formed owing to oligomer.

Comparative Example 3

Sulfonated polyaniline was synthesized as the aniline conducting polymeraccording to the known method [J. Am. Chem. Soc., (1991), 113,2665-2666]. The content of the sulfonic group in the polymer was 52%based on the aromatic ring.

Three parts by weight of the above sulfonated polyaniline was mixed with100 parts by weight of a 0.2 mole/liter aqueous sulfuric acid solutionat room temperature to prepare a conductive composition.

The solution thus obtained was coated onto a glass substrate by the spincoating method, but a film was not formed because the sulfonatedpolyaniline was insoluble in the 0.2 mole/liter aqueous sulfuric acidsolution.

FIG. 7 is the UV visible spectrum from 190 nm to 900 nm of the anilineconducting polymer synthesized in Comparative Example 3 (conventionalmethod) in a 0.2 mole/liter aqueous ammonia solution.

The polymer synthesized in Comparative Example 3 was insoluble inaqueous solutions and aqueous acidic solutions, so that its UV visiblespectrum could not be measured in these solutions.

The solubility of the conducting polymer synthesized in ComparativeExample 3 (conventional method) was as follows:

    ______________________________________                                        water               0         mg/ml                                           0.1 mole/liter aqueous sulfuric                                                                   0         mg/ml                                           acid solution                                                                 0.1 mole/liter aqueous ammonia                                                                    50        mg/ml.                                          ______________________________________                                    

Comparative Example 4

Sulfonated polyaniline was synthesized as the aniline conducting polymeraccording to the known method [J. Am. Chem. Soc., (1991), 113,2665-2666]. The content of the sulfonic group in the polymer was 52%based on the aromatic ring.

Three parts by weight of the above sulfonated polyaniline and 80 partsby weight of a water-soluble polyester resin (ARASTAR 300 produced byArakawa Kagaku Kogyo Co., Ltd.) were dissolved in 100 parts by weight ofwater at room temperature with stirring to prepare a conductivecomposition.

The solution thus obtained was coated onto a glass substrate by the spincoating method, but a film was not formed because the sulfonatedpolyaniline was insoluble in the aqueous solution.

Comparative Example 5

A polyaniline having a sulfonic group at the aromatic ring wassynthesized as the aniline conducting polymer according to the knownmethod (Japanese Patent Application No. 5-48540). Ten parts by weight ofaniline and 20 parts by weight of 2-aminoanisole-4-sulfonic acid werecopolymerized with ammonium peroxodisulfate in an acidic conditioncontaining sulfuric acid, to synthesize a polyaniline having a sulfonicacid group at the aromatic ring. The content of the sulfonic groups inthis polyaniline having a sulfonic group was 48%.

Three parts by weight of the above polyaniline having a sulfonic groupat the aromatic ring and 8 parts by weight of a water-soluble polyesterresin (ARASTAR 300 produced by Arakawa Kagaku Kogyo Co., Ltd.) weredissolved in 100 parts by weight of water at room temperature withstirring to prepare a conductive composition.

The solution thus obtained was coated onto a glass substrate by the spincoating method, but a film was not formed because the polyaniline havinga sulfonic group at the aromatic ring was insoluble in the aqueoussolution.

EXAMPLE 13

One hundred milimoles of o-aminobenzenesulfonic acid was dissolved in a4 moles/liter aqueous ammonia solution at 25° C. with stirring, and anaqueous solution containing 100 mmoles of ammonium peroxodisulfate wasadded dropwise thereto. After finish of addition, the reaction solutionwas further stirred at 25° C. for 12 hours, and the reaction product wasfiltered off, washed and dried to obtain 12 g of a polymer powder. Thispolymer had a volume resistance of 12.0 Ωcm.

Three parts by weight of the above polymer was dissolved in 100 parts byweight of a 0.2 mole/liter aqueous sulfuric acid solution at roomtemperature with stirring to prepare a conductive composition. Thesolution thus obtained was coated onto a glass substrate by the spincoating method and dried at 100° C. A film having a thickness of 0.1 μm,a smooth surface and a surface resistance of 2.5×10⁷ Ω/□, was obtained.

The result of measurement showed: number average molecular weight,150,000; weight average molecular weight, 190,000; Z average molecularweight, 210,000; and dispersion degree, MW/MN, 1.5, and MZ/MW, 1.3.

The polymer was added little by little to each of 10 ml of water, 10 mlof a 0.1 mole/liter aqueous sulfuric acid solution and 10 ml of a 0.1mole/liter aqueous ammonia. At a time when more polymer became to failto dissolve, each solution was filtered, and the amount dissolved wasmeasured to find that the solubility of the conducting polymersynthesized in Example 13 was as follows:

    ______________________________________                                        water                    230 mg/ml                                            0.1 mole/liter aqueous   225 mg/ml                                            sulfuric acid solution                                                        0.1 mole/liter aqueous ammonia                                                                         200 mg/ml.                                           ______________________________________                                    

FIG. 8 shows the IR spectrum of the conducting polymer synthesized inExample 13. The assignment of the IR spectrum is as follows:

sulfonic group: absorption in the vicinity of 1120, 1020 cm⁻¹.

ammonium salt of sulfonic group: absorption in the vicinity of 1400cm⁻¹.

skeleton of polymer: absorption in the vicinity of 1500 cm⁻¹.

EXAMPLE 14

One hundred milimoles of 3-methyl-6-amino-benzenesulfonic acid wasdissolved in a 4 moles/liter aqueous trimethylamine solution at 4° C.with stirring, and an aqueous solution containing 100 mmoles of ammoniumperoxodisulfate was added dropwise thereto. After finish of addition,the reaction solution was further stirred at 25° C. for 6 hours, and thereaction product was filtered off, washed and dried to obtain 10 g of apolymer powder.

This polymer was added to an acetone solution containing 1 mole/liter ofp-toluenesulfonic acid (PTS), and after stirring for 1 hour, thereaction product was filtered off, washed and dried to obtain 18 g ofthe powder of a sulfonic group-free polymer. This polymer had a volumeresistance of 12.5 Ωcm.

One part by weight of the above polymer was dissolved in 100 parts byweight of water at room temperature with stirring to prepare aconductive composition. Since the pH of the composition was about 3.5,it is presumed that about 80% or more of the sulfonic groups in thepolymer was in a free state. The solution thus obtained was coated ontoa glass substrate by the casting method and dried at 100° C. A filmhaving a thickness of 0.1 μm, a smooth surface and a surface resistanceof 5.0×10⁶ Ω/□, was obtained.

EXAMPLE 15

One hundred milimoles of 2-carboxyaniline (anthranilic acid) wasdissolved in a 4 moles/liter aqueous quinoline solution at 4° C. withstirring, and an aqueous solution containing 100 mmoles of ammoniumperoxodisulfate was added dropwise thereto. After finish of addition,the reaction solution was further stirred at 25° C. for 12 hours, andthe reaction product was filtered off, washed and dried to obtain 11 gof a polymer powder. This polymer had a volume resistance of 45 Ωcm.

Three parts by weight of the above polymer was dissolved in 100 parts byweight of water at room temperature with stirring to prepare aconductive composition.

Since the pH of the composition was about 6.0, it is presumed that about20% or more of the carboxyl groups in the polymer formed a salt.

The solution thus obtained was coated onto a PET film by the spincoating method and dried at 80° C. A film having a thickness of 0.1 μm,a smooth surface and a surface resistance of 3.0×10⁷ Ω/□, was obtained.

EXAMPLE 16

One hundred milimoles of 3-hydroxyanthranilic acid was dissolved in a 3moles/liter aqueous 2-methylpyridine (α-picoline) solution at 25° C.with stirring, and an aqueous solution containing 100 mmoles of ammoniumperoxodisulfate was added dropwise thereto. After finish of addition,the reaction solution was further stirred at 25° C. for 12 hours, andthe reaction product was filtered off, washed and dried to obtain 11 gof a polymer powder. This polymer had a volume resistance of 37 Ωcm.

Three parts by weight of the above polymer was dissolved in 100 parts byweight of water/isopropyl alcohol (7/3) at room temperature withstirring to prepare a conductive composition

The solution thus obtained was coated onto a glass substrate by the spincoating method and dried at 120° C. A film having a thickness of 0.1 μm,a smooth surface and a surface resistance of 7.0×10⁶ Ω/□, was obtained.

EXAMPLE 17

One hundred milimoles of 4-nitroanthranilic acid was dissolved in a 4moles/liter aqueous triethanolamine solution at 10° C. with stirring,and an aqueous solution containing 100 mmoles of ammoniumperoxodisulfate was added dropwise thereto. After finish of addition,the reaction solution was further stirred at 25° C. for 12 hours, andthe reaction product was filtered off, washed and dried to obtain 9.5 gof a polymer powder. This polymer had a volume resistance of 50 Ωcm.

Three parts by weight of the above polymer and 100 parts by weight of awater-soluble polyester resin (ARASTAR 300 produced by Arakawa KagakuKogyo Co., Ltd.) were dissolved in 100 parts by weight of water at roomtemperature with stirring to prepare a conductive composition.

The solution thus obtained was coated onto a PET film by means of agravure coater having a depth of 35 μm and dried at 70° C. A film havinga thickness of 0.5 μm, a smooth surface and a surface resistance of1.5×10⁷ Ω/□, was obtained.

EXAMPLE 18

One hundred milimoles of m-nitroanilinesulfonic acid was dissolved in a4 moles/liter aqueous piperidine solution at 25° C. with stirring, andan aqueous solution containing 100 mmoles of ammonium peroxodisulfatewas added dropwise thereto. After finish of addition, the reactionsolution was further stirred at 25° C. for 12 hours, and the reactionproduct was filtered off, washed and dried to obtain 6 g of a polymerpowder. This polymer had a volume resistance of 15 Ωcm.

Two parts by weight of the above polymer was dissolved in 100 parts byweight of a 0.2 mole/liter aqueous ammonia at room temperature withstirring to prepare a conductive composition.

The solution thus obtained was coated onto a PET film by the spincoating method and dried at 80° C. A film having a thickness of 0.1 μm,a smooth surface and a surface resistance of 1.0×10⁷ Ω/□, was obtained.

EXAMPLE 19

One hundred milimoles of 2-chloro-5-aminobenzenesulfonic acid wasdissolved in a 3 moles/liter aqueous sodium hydroxide solution at 4° C.with stirring, and an aqueous solution containing 100 mmoles of ammoniumperoxodisulfate was added dropwise thereto. After finish of addition,the reaction solution was further stirred at 25° C. for 6 hours, and thereaction product was filtered off, washed and dried to obtain 6 g of apolymer powder. This polymer had a volume resistance of 20 Ωcm. Thispolymer was added to an acetone solution containing 1 mole/liter ofp-toluenesulfonic acid (PTS), and after stirring for 1 hour, thereaction product was filtered off, washed and dried to obtain 4 g of thepowder of a sulfonic group-free polymer.

Three parts by weight of the above polymer was dissolved in 100 parts byweight of water at room temperature with stirring to prepare aconductive composition. This composition had a viscosity of 4.7 cp (at25° C.). This viscosity was measured with a Ubbelohde viscometer.

Since the pH of the composition was about 3.8, it is presumed that about80% or more of the sulfonic groups in the polymer was in a free state.

The solution thus obtained was coated onto a glass substrate by the spincoating method and dried at 80° C. A film having a thickness of 0.1 μm,a smooth surface and a surface resistance of 8.5×10⁶ Ω/□, was obtained.

Comparative Example 6

One hundred milimoles of o-aminobenzenesulfonic acid was suspended inwater at 4° C. with stirring, and an aqueous solution containing 100mmoles of ammonium peroxodisulfate was added dropwise thereto. Afterfinish of addition, the reaction solution was further stirred at 25° C.for 12 hours. The reaction solution was vacuum-distilled, and theconcentrated product was isolated, washed and dried to obtain 6 g of apolymer powder. This polymer had a volume resistance of >10⁶ Ωcm.

Three parts by weight of the above polymer powder was dissolved in 100parts by weight of water at room temperature with stirring to prepare aconductive composition.

The solution thus obtained was coated onto a PET film by the spincoating method, but a film was not formed.

Comparative Example 7

One hundred milimoles of 2-carboxyaniline (anthranilic acid) wassuspended in a 1 mole/liter aqueous sulfuric acid solution at 25° C.with stirring, and a 1 mole/liter aqueous sulfuric acid solutioncontaining 100 mmoles of ammonium peroxodisulfate was added dropwisethereto. After finish of addition, the reaction solution was furtherstirred at 25° C. for 12 hours. Thereafter, the reaction solution wasvacuum-distilled, and the concentrated product was isolated, washed anddried to obtain 3 g of a polymer powder. This polymer had a volumeresistance of >10⁶ Ωcm.

Three parts by weight of the above polymer was dissolved in 100 parts byweight of water at room temperature with stirring to prepare aconductive composition.

The solution thus obtained was coated onto a glass substrate by the spincoating method, but a film was not formed.

Comparative Example 8

One hundred milimoles of p-aminobenzenesulfonic acid and 40 mmoles ofaniline were suspended in a 1 mole/liter aqueous sulfuric acid solutionat 4° C. with stirring, and a 1 mole/liter aqueous sulfuric acidsolution containing 100 mmoles of ammonium peroxodisulfate was addeddropwise thereto. After finish of addition, the reaction solution wasfurther stirred at 25° C. for 12 hours, and the reaction product wasfiltered off, washed and dried to obtain 4.3 g of a polymer powder. Thispolymer powder had a volume resistance of 15 Ωcm.

Three parts by weight of the above aniline conducting polymer and 100parts by weight of water were mixed at room temperature to prepare aconductive composition.

The solution thus obtained was coated onto a glass substrate by the spincoating method, but a film was not formed because this polymer wasinsoluble in water.

The solubility of the conductive polymer synthesized in ComparativeExample 8 was as follows:

    ______________________________________                                        water                    0 mg/ml                                              0.1 mole/liter aqueous sulfuric                                                                        0 mg/ml                                              acid solution                                                                 0.1 mole/liter aqueous ammonia                                                                         3 mg/ml.                                             ______________________________________                                    

What is claimed is:
 1. An aniline conducting polymer comprising, as arepeating unit, at least one member selected from the group consistingof an alkoxy group-substituted aminobenzenesulfonic acid, an alkalimetal salt of alkoxy group-substituted aminobenzenesulfonic acid, anammonium salt of alkoxy group-substituted aminobenzenesulfonic acid anda substituted ammonium salt of alkoxy group-substitutedaminobenzenesulfonic acid in an amount of about 100%, and is a solidhaving a weight average molecular weight of about 1900 or more at roomtemperature and being soluble in acidic, basic and neutral aqueoussolutions and organic solvents.
 2. A soluble aniline conducting polymeraccording to claim 1 comprising a repeating unit represented by theformula (1), ##STR11## wherein each of A¹, A², A³ and A⁴ is a groupindependently selected from the group consisting of hydrogen, an alkalimetal, ammonium and a substituted ammonium, R represents a C₁ -C₁₂straight-chain or branched alkyl group, X represents a number of from 0to 1, and n represents a polymerization degree which is a number of from3 to 5000,and is a solid having a weight average molecular weight ofabout 1900 or more at room temperature.
 3. A soluble aniline conductingpolymer according to claim 1 having a surface resistance not more thanan order of 10⁸ Ω/□ when it is measured at a film thickness of 0.1 μm.4. A soluble aniline conducting polymer according to claim 1 which issoluble in aqueous acidic solutions.
 5. A conductive compositioncomprising a water-soluble aniline conducting polymer (a) and a solvent(b), said conducting polymer (a) comprising, as a repeating unit, atleast one member selected from the group consisting of an alkoxygroup-substituted aminobenzenesulfonic acid, an alkali metal salt ofalkoxy group-substituted aminobenzenesulfonic acid, an ammonium salt ofalkoxy group-substituted aminobenzenesulfonic acid and a substitutedammonium salt of alkoxy group-substituted aminobenzenesulfonic acid inan amount of about 100%, and being a solid having a weight averagemolecular weight of about 1900 or more at room temperature and beingsoluble in acidic, basic and neutral aqueous solutions and organicsolvents.
 6. A conductive composition according to claim 5, wherein saidwater-soluble aniline conducting polymer comprises a repeating unitrepresented by the formula (1): ##STR12## wherein each of A¹, A², A³ andA⁴ is a group independently selected from the group consisting ofhydrogen, an alkali metal, ammonium and a substituted ammonium, Rrepresents a C₁ -C₁₂ straight-chain or branched alkyl group, Xrepresents a number of from 0 to 1, and n represents a polymerizationdegree which is a number of from 3 to 5000,and is a solid having aweight average molecular weight of about 1900 or more at roomtemperature.
 7. A conductive composition according to claim 5, whereinsaid water-soluble aniline conducting polymer is obtained bypolymerizing at least one member selected from the group consisting ofan alkoxyl group-substituted aminobenzenesulfonic acid represented bythe formula (3): ##STR13## wherein R represents a C₁ -C₁₂ straight-chainor branched alkyl group,its alkali metal salt, ammonium salt andsubstituted ammonium salt in a basic compound-containing solution usingan oxidizing agent.
 8. A conductive composition according to claim 5,which contains as an additional component at least one polymer compound(c) selected from the group consisting of a water-soluble polymercompound and a polymer compound which forms an emulsion in an aqueoussolution.
 9. A conductive composition according to claim 5, whichcontains as an additional component at least one nitrogen-containingcompound (d) selected from the group consisting of an amine and aquaternary ammonium salt.
 10. A conductive composition according toclaim 8, which contains as an additional component at least onenitrogen-containing compound (d) selected from the group consisting ofan amine and a quaternary ammonium salt.
 11. A conductive compositionaccording to claim 5, which contains a surface active agent (e) as anadditional component.
 12. A conductive composition according to claim 8,which contains a surface active agent (e) as an additional component.13. A conductive composition according to claim 10, which contains asurface active agent (e) as an additional component.
 14. An anilineconducting polymer produced by a process comprising polymerizing atleast one member selected from the group consisting of an alkoxygroup-substituted aminobenzenesulfonic acid represented by the formula(3): ##STR14## wherein R represents a C₁ -C₂ straight-chain or branchedalkyl group, an alkali metal salt of alkoxy group-substitutedaminobenzenesulfonic acid, an ammonium salt of alkoxy group-substitutedaminobenzenesulfonic acid and a substituted ammonium salt of alkoxygroup-substituted aminobenzenesulfonic acid in an amount of about 100%,in a basic compound-containing solution using an oxidizing agent.